Dyestuffs of the anthraquinone series



Patented Nov. 9, 1948 DYESTUFFS OF THE AN THRAQUINON E I SERIES Samuel von Allmen and Hans Eggenberger, Base-1,. Switzerland, assignors to Sandoz Limited, Basel, Switzerland, a Swiss firm V No Drawing.

Application September 19, 1945,

Serial No. 617,455. In Switzerland October 19,

4 Claims. (Cl. 260371) The present invention relates to new dyestuffs of the anthraquinone series which dye animal fibres in brilliant blue shades possessing an improved fastness to light and which do not change their shade in the artificial light.

It is known that anthraquinone compounds of the general formula (II) NH:

NHR

wherein It stands for a substituted or unsubstituted hydroaromatic group, dye animal fibres in very brilliant blue shades (of. for instance (Bierman Patents 456,114; 554,324.; 569,879).

It has now been found that new valuable anthraquinone dyestuifs can be produced by condensing anthraquinone compounds of the general formula wherein Y stands for halogen or a sulpho group and wherein one of the X is a sulphonic group, the other X being hydrogen, with halogen-free hydroaromatic amines.

The dyestuffs prepared from these starting products give very brilliant shades on animal fibres and, as compared with the known dyestuffs cited above, they possess an improved fastness to light and an improved stability of the shade in i the artificial light",

The present process is characterized in. that the starting products are heated togetherat amoderated temperature in an aqueous or organic solvent medium or mixtures of these media in the presence of a catalyst, like copper or copper salt. and of an acid binding agent. 7

The anthraquinone compounds used as starting products are for example 1-amino-4-bromanthraquinone-2.6-disulphonic acid, l-amino-4-ch1oranthraquinone-2.6-disu1phonic acid, 1-amino-4- brornanthraquinone 2.7 disulphonic acid, 1- amino-4 chloranthraquinone 2.7 disulphonic acid or their salts. It is also possible to use as starting compounds a mixture of these different anthraquinone compounds.

The hydroaromatic bases which are free from halogen must contain the amino group linked to the hydrogenated ring; such bases arefor instance the hexahydroaniline, -toluidine, -xylidine, the 1.2.3.4-tetrahydro-1- or 2-naphthyl amines and the like.

The same dyestuffs can also be preparedby condensing, in the presence of a catalyst and of an acid binding agent, the 1-amino-2.4-diha1ogenanthraquinone-G- or -7-sulphonic acids, their salts of their mixtures with the above said hydroar-omatic amines, and after the separation of the intermediate products thus formed, by subjecting them to a treatment with a sulphite in order to replace the fi-halogen atom by a sul phonic acid group.

The dyestuffs prepared according to the present process are very easily soluble in water and dye wool as well as other animal fibres and also artificial fibres, like nylon, in beautiful blue shades of a great purity. These dyeings possess an excel lent-fastnessto light and do not change their shade in the artificial light.

a The following examples, in which the parts are by weight, illustrate the present invention:

Example 1 v 13 parts of the sodium salt of l-aminol-brom- "an'thraquinone-2.6 disulfonic acid are slowly added at 65 C. in the course of 9 hours under "stirring'to a, mixture consisting'of 80 parts of water, 34 parts of hexahydroaniline, 4 parts of a 33% aqueous sodium hydroxide solution, 0.1 part of copper powder, whereby a nitrogen stream is allowed to flow in simultaneously. After the additionof the anthraquinone derivative stirring iscontinued for further 3 hours at 65 C. and then the blue condensation mass subjected to the steam-distillation in order to regenerate the excess' of hexahyd'roan'iline. Thereon the dyestuff is salted out and worked up in the usual manner.

In dry form it is a blue powder, easily soluble in water, dyeing wool and other animal fibres and artificial fibres like nylon in beautiful blue shades possessing a great purity. The dyeings are fast to light and do notchange in the artificial light.

If, instead of the sodium salt of 1-amino-4- bromanthraquinone-2.6-disulphonic acid, a corresponding quantity of the sodium salt of 1- amino 4 chloranthraquinone-Zfi disulphonic acid is used and the condensation conducted in the manner described above. an identical dyestufi will be obtained.

Example 2 If, instead of 13 parts of the sodium salt of 1-amino-4-bromanthraquinone 2,6 disulphonic acid, there is used the same quantity of its isomer containing the sulphonic groupsin 2.7-positions, and worked up in the manner described in Example 1, a blue dyestuff will be obtained which is an isomeric compound of that of Example 1 and possesses very similar properties.

Example 3 13 parts of the mixture of-thersodiumi saltsiiof- 1-amino-4-bromanthraquinone 2;6- and 237 -disulphonic acid are condensed in the manner described in Example 1 with Siparts ofhexahydroaniline. Thus a mixture of'the'isomeric dyestuffs described in Examples 1 and 2 will be obtained.

Example 4 13:.parts of the sodium salt of 1-amino-4-bromanthraquinone-2.6 disulfonic acid are added at 65C. under good stirring in l2'-hoursto a'mixture OfT SO IJaItS of water, 40 parts-of hexahydro-otoluidine, '4 parts of 3.133% aqueous-sodiumhyidroxide solution, 0.2 partiof' copper sulfate, 2.

moderate nitrogen stream being introduced simultaneously. Thereupon the mass. is stirred for .Iurther 3 hours at 65 C. and the dyestufi worked up in the usual way. 'It dyes woolin beautiful blue shades.

Example 5 l3 parts of the sodium salt of 1-amino-4-brom- 'anthraquinone 2.6 disulfanic acid are slowly introduced within 18 hours understirring into a mixtureof 60 C. consisting'of 60 parts of water,

60 parts of Z-amino-l.2.3A-tetrahydronaphthalene, 4 parts of a 33% aqueous sodium hydroxide solution,0.2-part of copper powder and 20 parts of ethyl-alcohol, a moderate nitrogen stream being allowed to flow in simultaneously. After a'further v6 hours stirring at 60 C. the condensation is terminated. The dyestuif is worked up in the manner described above. In I dry state it is a blue powder being easily soluble in water, "dyeing wool and other animal fibres in blue shades of a greatpurity and of a goodfastness to light.

The isomeric dyestufi possessing the sulphonic acid groups in 2 and 7-:positions possesses similar properties.

A similar dyestufi will also be obtained, if

.2 amino 1.2.3.4 --tetrahydronaphthalene is ,rezplacedfby its'isomer containing the aminosgroup IiIIi-l DOSitiDl-l.

Example *6 The same edyestuff' as described in Example 1 maybe obtained by condensing in the same manner 11 parts of the potassium saltof 1-,a1mino-.'

.. 2- -dibromanthraquinonee6-sulfonic acid .withi34 -parts of hexahydroaniline and transforming "the :dyestuff'thusobtained into the product, sulfonated jin z position, bya treatment.witbsulflte according "toithe usual. methods.

:Whatweclaim, is: -1. ;An ;anthraquinone dyestufftof theiformula 'O IFH: l

4 wherein one X stands for a sulfo group and the other X stands for hydrogen, and wherein R stands for a member selected from the group consisting of hexahydrophenyl, hexahydrotolyl, hexahydroxylyl and ac-tetrahydronaphthyl.

2; The anthraquinone dyestufiof :the formula q-wl'iicl'1 dyestufi dyes animal fibres into brilliant blue shades-being fast to light and stable in the artificial light.

v3. The anthraquinone dyestufif of the formula HOaS baron: which dyestuff dyes animal fibres into brilliant blue shades being fast to light and stable in the artificial light.

4. The anthraquinone dyestufl' of'the formula LO INH;

i 7 CH2 whichv dyestufi" dyes animal .fibres into brilliant blue shades being fast to light and stable in the artificial light.

SAMUEL VON ALLMEN.

HANS EGGENBERGERQ REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date "1,688,256 Weinand Oct;16, 1928 1,821,043 Weinand Sept. 1, 1931 1,843,308 Weinand -Feb. 2, 1932 .'2,067-,469 Weinande't al.- Jan. 12, 1937 FOREIGN PATENTS Number "Country Date 53813954 "Great Britain Oct. 3,1932 462,694 Great Britain Mar.15, 1 937 

